Polyoxyalkylenepolyols and process for producing ring-opened polymer

ABSTRACT

A polyoxyalkylene polyol or monool (I) of the general formula (1) below, in which not less than 40% of the terminally located hydroxyl-containing groups, namely —AO—H groups, are primary hydroxyl-containing groups of the general formula (2) below, or; 
     a method of producing ring-opening polymerization products, by subjecting a heterocyclic compound to ring-opening addition polymerization with an active hydrogen-containing compound, using as a catalyst tris(pentafluorophenyl)borane, tris(pentafluorophenyl)aluminum, etc. 
     
       
         R 1 —[—(ZO) p —(AO) q —H] m ( 1 )

TECHNICAL FIELD

The present invention relates to polyoxyalkylene polyols or monoolshaving the proportion of terminal primary hydroxyl groups of not lessthan 40%; to a method of preparing ring-opening polymerization productsby ring-opening addition polymerization of a heterocyclic compound; andto polyol compositions for use as polyol components for polyurethaneresins, epoxy resins and like thermosetting resins. More particularly,it relates to polyoxyalkylene polyols having increased reactivity withisocyanato groups or the like without impairing their hydrophobicity; toa method of effecting ring-opening polymerization of cyclic compounds inthe presence of a specific catalyst; and to the use of said compounds aspolyol components for thermosetting resins.

BACKGROUND ART

Polyols such as polyoxyalkylene polyols obtained by ring-openingreaction of a monoepoxide, such as an alkylene oxide, with an activehydrogen-containing compound are in wide use as starting materials forthermosetting resins such as polyurethanes, as surfactants, aslubricants and in other fields of application.

The method so far widely used for the production of polyethers comprisesreacting a monoepoxide in the presence of an alkaline catalyst. Used asthe alkaline catalyst are alkali metal compounds such as potassiumhydroxide and sodium hydroxide. As an alternative, the method is alsoknown which comprises carrying out the reaction of a monoepoxide using aBF₃ complex, zinc hexacyanocobaltate or a like composite metal cyanidecomplex as the catalyst.

Polyoxyalkylene polyols obtained by ring-opening reaction of anα,β-epoxides such as propylene oxide, epichlorohydrin, styrene oxide orlaurylene oxide in the presence of such catalyst have very lowproportion of terminal primary hydroxyl groups (generally not more than2% when potassium hydroxide is used, for instance), most of the terminalhydroxyl groups being secondary hydroxyl groups. Therefore, such polyolshave insufficient reactivity for use as polyol components forthermosetting resins. For example, they have low reactivity withisocyanate groups in isocyanate-containing compounds (tolylenediisocyanate etc.) and have insufficient reactivity when they are usedas polyol components for urethane resins.

For securing sufficient reactivity with isocyanate groups, the terminalhydroxyl groups is required to be primary hydroxyl groups. For thispurpose, a method is known which comprises performing ring-openingreaction of alkylene oxides to obtain polyoxyalkylene polyols, and thensubjecting ethylene oxide to ring-opening reaction therewith, thusgenerating terminal primary hydroxyl groups. However, since thepolyethylene oxide portions are hydrophilic, such method reduces thehydrophobicity of polyoxyalkylene polyols. When such polyols are used,there arises a problem in that the physical and other characteristics ofthe resulting urethane resins vary widely depending on humidity.

On the other hand, for ring-opening polymerization of carbonates,thiocarbonates, dithiocarbonates and like cyclic compounds, a method hasbeen used which comprises effecting ring-opening polymerization in thepresence of an acid catalyst such as BF₃.

However, this method of producing ring-opening polymerization products,which comprises effecting ring-opening polymerization of carbonates,thiocarbonates, dithiocarbonates and like cyclic compounds in thepresence of such a catalyst, has a problem in that carbon dioxide,carbon oxide sulfide, carbon disulfide or the like is eliminated duringring-opening addition polymerization of such cyclic compounds, leadingto low yields of the ring-opening polymerization products derived fromthe cyclic compounds. In addition, in the step of ring-openingpolymerization, such a catalyst must be used in an amount almostequivalent to growing chain terminals, so that a large quantity of thecatalyst remains in the polymers produced. In certain fields ofapplication of the ring-opening polymerization products thus obtained,the residual catalyst has significant adverse effects, hence it isnecessary to remove the catalyst by treatment following the ring-openingpolymerization.

In view of the foregoing, the present invention has its object toprovide polyol compositions having sufficient reactivity for use asmaterials for thermosetting resins without impairing the hydrophobicityof polyoxyalkylene polyols; polyoxyalkylene polyols suited for use inthis polyol compositions; a method of producing this polyoxyalkylenepolyols; and a method of producing ring-opening polymerization productsby subjecting a cyclic compound to ring-opening addition polymerizationin the presence of a specific catalyst.

SUMMARY OF INVENTION

The present inventors made intensive investigations in an attempt tosolve the above problems and, as a result, found that:

(1) polyoxyalkylene polyols having the proportion of terminal primaryhydroxyl groups of not less than 40% have sufficient reactivity aspolyol components for thermosetting resins while retaining thehydrophobicity thereof;

(2) such polyoxyalkylene polyols having the proportion of terminalprimary hydroxyl groups of not less than 40% can be obtained by addingan epoxy containing compound to an active hydrogen-containing compoundin the presence of a catalyst having a specific chemical structure and;

(3) the yield is very high when a cyclic compound is subjected toring-opening addition polymerization in the presence of a specificcatalyst. These findings have now led to completion of the presentinvention.

Thus, the present invention consists in polyoxyalkylene polyols ormonools (I) of the general formula (1) below, characterized in that notless than 40% of the terminally located hydroxyl-containing groups,namely —AO—H groups, are primary hydroxyl-containing groups of thegeneral formula (2) below:

R¹—[—(ZO)_(p)—(AO)_(q)—H]_(m)(1)

wherein:

in the formula (1), R¹ is a group having a valence of m as derived froma compound selected from the group consisting of water, an alcoholcompound, a phenol compound, an amino-containing compound, acarboxyl-containing compound, a thiol-containing compound and aphosphoric acid compound by removal of its active hydrogen atom oratoms; Z is an alkylene group containing 2 to 12 carbon atoms or acycloalkylene group containing 6 to 12 carbon atoms, each of which maycontain at least one halogen atom or aryl group or both as substituents;A is an alkylene group containing 3 to 12 carbon atoms or acycloalkylene group containing 6 to 12 carbon atoms, each of which maycontain at least one halogen atom or aryl group or both as substituents;m is an integer of 1 or 2 to 100; p is an integer of 0 or 1 or more andq is an integer of 1 or more, p+q being equal to 1 to 200; and in theformula (2), R² is an alkyl group containing 1 to 10 carbon atoms or anaryl group containing 6 to 10 carbon atoms, each of which may besubstituted by a halogen atom or atoms.

The present invention also consists in a method of producingring-opening polymerization products, which comprises subjecting aheterocyclic compound (d) of the general formula (5) below toring-opening addition polymerization with an active hydrogen-containingcompound (b) of the general formula (3) below in the presence of atleast one catalyst (c) selected from the group consisting of compoundshaving the general formula (4-1) below, compounds of the general formula(4-2) below and compounds of the general formula (4-3) below:

R¹—[—(ZO)_(p)—H]_(m)  (3)

X—(—R³)₂  (4-1)

wherein:

in the formula (3), R¹ is a group having a valence of m as derived froma compound selected from the group consisting of water, an alcoholcompound, a phenol compound, an amino-containing compound, acarboxyl-containing compound, a thiol-containing compound and aphosphoric acid compound by removal of its active hydrogen atom oratoms; Z is an alkylene group containing 2 to 12 carbon atoms or acycloalkylene group containing 6 to 12 carbon atoms, each of which maycontain at least one halogen atom or aryl group or both as substituents;m is an integer of 1 or 2 to 100; and p is an integer of 0 or 1 to 199;

in each of the formulae (4-1), (4-2) and (4-3), X represents a boronatom or aluminum atom; F represents a fluorine atom; and R³ represents asubstituted or unsubstituted phenyl group of the general formula (6)below and/or a tertiary alkyl group of the general formula (7) below;

wherein, in the formula (6), Y represents a hydrogen atom, an alkylgroup containing 1 to 4 carbon atoms, a halogen atom, a vitro group or acyano group; and k represents an integer of 0 to 5, provided that when kis 2 or more, a plurality of Y groups may be the same or different;

wherein R¹ R⁵ and R⁶ each independently represents an alkyl groupcontaining 1 to 4 carbon atoms and when there are a plurality of R¹groups, they may be the same or different.

in the formula (5), R is an alkylene group containing 3 to 12 carbonatoms, which may contain at least one halogen atom or aryl group or bothas substituents; Q is a divalent organic group selected from the groupconsisting of —O—, —S—, —NH—, —O(CO)O—, S(CO)O—, —O(CS)O—, —O(CO) S—,—O(CS)S—, —S(CS)O——S(CO)S—, —S(CO)S—, —COO—, —CSO—, —COS—, —CSS—, —CONN—and —N═C(—R⁷)—O—in which R⁷ represents an alkyl group containing 1 to 12carbon atoms, a cycloalkyl group containing 1 to 12 carbon atoms, whichmay be substituted by an alkyl group, or an aryl group containing 1 to12 carbon atoms, which may be substituted by a halogen atom.

The present invention further consists in:

polyol compositions (III) for the production of thermosetting resins,which comprise the above polyoxyalkylene polyols or monools (I);

ring-opening polymerization products produced by the production methodmentioned above;

in particular, polyol compositions (II) for the production ofthermosetting resins, which comprise said ring-opening polymerizationproducts, and;

a method of producing polyurethane resins by reacting polyol componentsand polyisocyanates (e) in which said polyol compositions (II) or (III)are used as the polyol components.

DETAILED DESCRIPTION OF THE INVENTION

According to its first aspect, the present invention is concerned withpolyoxyalkylene polyols or monools (I) of the above general formula (1),in which not less than 40% of terminally located hydroxyl-containinggroups, namely —AO—H groups, are primary hydroxyl-containing groups ofthe above general formula (2).

In the formula (1), R¹ is a group having a valence of m as derived froma compound selected from the group consisting of water, an alcoholcompound, a phenol compound, an amino-containing compound, acarboxyl-containing compound, a thiol-containing compound and aphosphoric acid compound by removal of its active hydrogen atom oratoms, and m is an integer of 1 (monools) or 2 to 100 (polyols).

R¹ may be a group derived from a compound (a) having m active hydrogenatoms) by removal of said active hydrogen atom(s). As such compound (a),there may be mentioned for example hydroxyl-containing compounds,amino-containing compounds, carboxyl-containing compounds,thiol-containing compounds, phosphoric acid compounds; compounds havingtwo or more active hydrogen-containing functional groups within onemolecule; and mixtures of two or more of these compounds.

As said hydroxyl-containing compounds, there may be mentioned, amongothers, water, monohydric alcohols, polyhydric (dihydric to octahydric)alcohols, phenols and polyphenols. More specifically, there may bementioned monohydric alcohols such as methanol, ethanol, butanol andoctanol; dihydric alcohols such as ethylene glycol, propylene glycol,1,1-butylene glycol, 1,1-butanediol, 1,6-hexanediol,3-methylpentanediol, diethylene glycol, neopentyl glycol,1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxyethyl)benzene and2,2-bis(4,4′-hydroxycyclohexyl)propane; trihydric alcohols such asglycerol and trimethylolpropane; tetra- to octa-hydric alcohols such aspentaerythritol, diglycerol, α-methylglucoside, sorbitol, xylitol,mannitol, dipentaerythritol, glucose, fructose and sucrose; phenols suchas phenol and cresol; polyphenols such as pyrogallol, catechol andhydroquinone; bisphenols such as bisphenol A, bisphenol F and bisphenolS; polybutadiene polyols; castor oil-derived polyols; and polyfunctionalpolyols (e.g. with two to 100 functional groups) such as hydroxyalkyl(meth)acrylate (co)polymers and poly vinyl alcohol)s, among others.

As said amino-containing compounds, there may be mentioned, for example,amines, polyamines, amino alcohols and the like. More specifically,there may be mentioned ammonia; monoamines such as alkylaminescontaining 1 to 20 carbon atoms (e.g., butylamine) and aniline;aliphatic polyamines such as ethylenediamine, trimethylenediamine,hexamethylenediamine and diethylenetriamine; heterocyclic polyaminessuch as piperazine and N-aminoethylpiperazine; alicyclic polyamines suchas dicyclohexylmethanediamine and isophoronediamine; aromatic polyaminessuch as phenylenediamine, tolylenediamine, diethyltolylenediamine,xylylenediamine, diphenylmethanediamine, diphenyl ether diamine andpolyphenylmethanepolyamine; alkanolamines such as monoethanolamine,diethanolamine, triethanolamine and triisopropanolamine; polyamidepolyamines obtained by condensation of a dicarboxylic acid and an excessof a polyamine; polyether polyamines; hydrazines (hydrazine,monoalkylhydrazines, etc.), dihydrazides (succinic dihydrazide, adipicdihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, etc.),guanidines (butylguanidine, 1-cyanoguanidine, etc.); dicyandiamide andthe like; and mixtures of two or more of these.

As said carboxyl-containing compounds, there may be mentioned aliphaticmonocarboxylic acids such as acetic acid and propionic acid; aromaticmonocarboxylic acids such as benzoic acid; aliphatic polycarboxylicacids such as succinic acid and adipic acid; aromatic polycarboxylicacids such as phthalic acid, terephthalic acid and trimellitic acid; andpolycarboxylic acid polymers (with 2 to 100 functional groups) such asacrylic acid (co)polymers, among others.

As said thiol-containing compounds, typically polythiol compounds, theremay be mentioned, among others, divalent to octavalent polythiols. Morespecifically, there may be mentioned ethylene dithiol, propylenedithiol, 1,3-butylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol,3-methylpentanedithiol and the like.

As said phosphoric acid compounds, there may be mentioned phosphoricacid, phosphorous acid and phosphoric acids.

Among these active hydrogen-containing compounds (a),hydroxyl-containing compounds, amino-containing compounds and water arepreferred, among which alcohols and amines are more preferred.

In the above formula (1), Z is an alkylene group containing 2 to 12carbon atoms or a cycloalkylene group containing 6 to 12 carbon atoms,and may contain at least one halogen atom or aryl group or both assubstituents. More specifically, there may be mentioned, among others,ethylene, propylene, butylene, chloropropylene bromopropylene,laurylene, phenylethylene, chlorophenylethylene, 1,1-cyclohexylene andthe like, and combinations of two or more of these. Preferred among themare propylene, butylene and ethylene groups and particularly preferredare propylene and butylene groups. When consideration is given to themaintenance of the hydrophobicity of the product polyoxyalkylene polyolsor monools (I), the use of propylene, butylene or the like group or thecombined use of ethylene and another alkylene group is recommended.

In the above formula (1), A is an alkylene group containing 3 to 12carbon atoms or a cycloalkylene group containing 6 to 12 carbon atoms,and may contain at least one halogen atom or aryl group or both assubstituents. More specifically, there may be mentioned for examplepropylene, butylene, chloropropylene, bromopropylene, laurylene,phenylethylene, chlorophenylethylene, 1,2-cyclohexylene and the like,and combinations of two or more of these. When ethylene group is used,it is preferably used in combination with another alkylene group fromthe viewpoint of the hydrophobicity of the resulting polyoxyalkylenepolyols or monools (I).

In the present invention, the —AO—H groups, which are terminally locatedhydroxyl-containing groups among groups of —(AO)_(q)—H in the abovegeneral formula (1), include two types, namely primaryhydroxyl-containing groups of the above general formula (2) andsecondary hydroxyl-containing groups of the general formula (2′) givenbelow. The polyoxyalkylene polyols or monools (I) according to the firstaspect of the present invention are characterized in that the content ofthe primary hydroxyl-containing groups of the above general formula (2)is not less than 40% preferably not less than 60%, relative to the totalsum of terminal hydroxyl groups in the polyoxyalkylene polyols ormonools (I).

In the above formulae (2) and (2′), R² represents an alkyl groupcontaining 1 to 10 carbon atoms or an aryl group containing 6 to 10carbon atoms, each of which may be substituted by a halogen atom oratoms. More specifically, there may be mentioned for example linearalkyl groups such as methyl, ethyl and propyl; branched alkyl groupssuch as isopropyl; phenyl and substituted phenyl groups such asp-methylphenyl; substituted alkyl groups such as chloromethyl,bromomethyl, chloroethyl and bromoethyl; substituted phenyl groups suchas p-chlorophenyl and p-bromophenyl, and combinations of two or more ofthese.

The subscript p is an integer of 0 or 1 or more, and q is an integer of1 or more, the sum p+q being 1 to 200. Generally, p is an integer of 0to 199, preferably 0 to 100, q is generally an integer of 1 to 200,preferably 1 to 100, and p+q is preferably 1 to 100.

The polyoxyalkylene polyols or monools (I) of the present inventiongenerally have a number average molecular weight of 400 to 100,000,preferably 400 to 20,000. This molecular weight is adequately selectedaccording to the field of use, for example according to the physicalcharacteristics required of thermosetting resins such as polyurethaneresins to be produced therefrom.

As specific examples of the polyoxyalkylene polyols (I-1) or monools(I-2), there may be mentioned for example water-derived propylene oxideadducts, methanol derived propylene oxide adducts, glycerol-derivedpropylene oxide adducts, ammonia-derived propylene oxide adducts,water-derived butylene oxide adduct-derived propylene oxide adducts,methanol-derived butylene oxide adduct-derived propylene oxide adducts,glycerol-derived butylene oxide adduct-derived propylene oxide adducts,ammonia-derived butylene oxide adduct-derived propylene oxide adducts,and the like.

As mentioned hereinabove, the proportion of primary hydroxyl-containinggroups of the above general formula (2) relative to the total hydroxylgroups located terminally in the polyoxyalkylene polyols or monools (I)of the present invention (in the present specification, said proportionis also referred to as “proportion of terminal primary hydroxyl groups”)is not less than 40% When it is less than 40%, the reactivity isinsufficient for use as polyol components. Preferably, said proportionis not less than 60%. This proportion of terminal primary hydroxylgroups is calculated based on the data obtained by ¹H-NMR measurementfollowing pretreatment of the sample, i.e. esterification.

An example of said ¹H-NMR measurement is specifically described in thefollowing.

Sample preparation

About 30 mg of the sample is weighed in a sample tube for NMR with 5-mmdiameter, and about 0.5 ml of deuterated solvent is added to dissolvethe sample. Then, about 0.1 ml of trifluoroacetic anhydride is added andthe resulting solution is used as a sample for analysis. Said deuteratedsolvent is, for example, deuterated chloroform, deuterated toluene,deuterated dimethyl sulfoxide, deuterated dimethylformamide or the likeand a suitable one is selected so that the sample can be dissolvedtherein.

NMR measurement

Their ¹H-NMR measurements are carried out under ordinary conditions.

Calculation of the proportion of terminal primary hydroxyl groups

Upon the above-mentioned pretreatment, the terminal hydroxyl groups ofthe sample polyoxyalkylene polyol react with the trifluoroaceticanhydride added to form trifluoroacetate ester derivatives. As a result,a signal from a primary hydroxyl-bound methylene group is observed atabout 4.3 ppm while a secondary hydroxyl-bound methylene group gives asignal at about 5.2 ppm. The proportion of terminal primary hydroxylgroups is calculated according to the equation below:

Proportion of terminal primary hydroxyl groups (%)=[a+2×b)]×100

wherein a is the integral value for the signal at about 4.3 ppm fromprimary hydroxyl-bound methylene groups; and b is the integral value forthe signal at about 5.2 ppm from secondary hydroxyl-bound methylenegroups.

The active hydrogen-containing compound (b) to be used in the method ofproducing ring-opening polymerization products according to the presentinvention is represented by the above general formula (3). In thegeneral formula (3), R¹ is as defined above and, as examples thereof,those mentioned above can be recited.

In the general formula (3), Z is an alkylene group containing 2 to 12carbon atoms or a cycloalkylene group containing 6 to 12 carbon atomsand may contain at least one halogen atom or aryl group or both assubstituents. As for Z, too, those recited above may be mentioned asexamples thereof.

In the formula (3), p is an integer of 0 or 1 to 199, preferably aninteger of 0 to 100. And m is an integer of 1 or 2 to 100.

As specific examples of the active hydrogen-containing compound (b) inwhich p is 0, there may be mentioned for instance the same ones asrecited above in relation to the first aspect of the present invention,as the compound (a) having m active hydrogen(s).

When p is 1 or more, there may be mentioned, among others, compoundsderived from said compound in which p is 0, namely the compound (a)having m active hydrogen atoms, by addition reaction of an alkyleneoxide containing 2 to 12 carbon atoms; for example addition products ofpropylene oxide, butylene oxide or the like to hydroxyl-containingcompounds, amino-containing compounds and the like. As specificexamples, there may be mentioned water-derived propylene oxide adducts(polyoxypropylene glycol), methanol-derived propylene oxide adducts,glycerol-derived propylene oxide adducts, water-derived butylene oxideadducts, methanol-derived butylene oxide adducts, glycerol-derivedbutylene oxide adducts, ammonia-derived propylene oxide adducts andammonia-derived butylene oxide adducts, among others.

Said catalyst (c) is a compound represented by either the above generalformula (4-1), (4-2) or (4-3). This catalyst can be used forring-opening addition polymerization of cyclic ether compounds,carbonates, dithiocarbonates and like heterocyclic compounds, to therebyobtain ring-opening polymerization products in good yields. Inparticular this can be used for ring-opening addition polymerization ofepoxy-containing compounds, thus obtaining polyoxyalkylene polyols withhigh proportion of terminal primary hydroxyl groups, which has so farnever been attained.

In each of the above formulae (4-1), (4-2) and (4-3), X represents aboron atom or aluminum atom and is preferably a boron atom.

In formulae (4-1), (4-2) and (4-3), R³ represents the substituted orunsubstituted phenyl group of the above general formula (6) or thetertiary alkyl group of the above general formula (7), When there are aplurality of R¹ groups, they may be the same or different.

In the above general formula (6), Y represents a hydrogen atom, an alkylgroup containing 1 to 4 carbon atoms, a halogen atom, a nitro group or acyano group. Preferred among these are a hydrogen atom, a halogen atomand a cyano group. More preferred are a halogen atom and a cyano group.

The subscripts k represents an integer of 0 to 5.

As specific examples of the phenyl or substituted phenyl group of theabove general formula (6), there may be mentioned phenyl,pentafluorophenyl, p-methylphenyl, p-cyanophenyl and p-nitrophenyl,among others. Preferred are phenyl, pentafluorophenyl and p-cyanophenyland more preferred are phenyl and pentafluorophenyl.

R⁴, R⁵ and R⁶ in the above general formula (7) each independentlyrepresents an alkyl group containing 1 to 4 carbon atoms. Specifically,there may be mentioned methyl, ethyl, propyl and isopropyl, amongothers.

As specific examples of the above tertiary alkyl group of the generalformula (7), there may be mentioned t-butyl and t-pentyl, among others.

In the present invention, said catalyst (c) specifically includes, amongothers, triphenylborane, diphenyl-t-butylborane, tri(t-butyl borane,triphenylaluminum, diphenyl-t-butylaluminum, tri(t-butyl)aluminum,tris(pentafluorophenyl)borane, bis(pentafluorophenyl)-t-butylborane,tris(pentafluorophenyl)aluminum, bis(pentafluorophenyl)-t-butylaluminum,bis(pentafluorophenyl)fluoroborane, di(t-butyl)fluoroborane,(pentafluorophenyl)difluoroborane, (t-butyl)difluoroborane,bis(pentafluoro-phenyl)fluoroaluminum, di (t-butyl)fluoroaluminum,(pentafluorophenyl)difluoroaluminum, (t-butyl)difluoroaluminum and thelike. Preferred are triphenylborane, triphenylaluminum,tris(pentafluorophenyl)borane and tris(pentafluorophenyl)aluminum andmore preferred are tris(pentafluorophenyl)borane andtris(pentafluorophenyl)aluminum.

The heterocyclic compound (d) to be subjected to addition reactionaccording to the present invention is represented by the above generalformula (5). As specific examples of said heterocyclic compound (d),there may be mentioned, among others, cyclic ethers, such as ethyleneoxide, propylene oxide, butylene oxide, styrene oxide, oxetane andtetrahydrofuran; cyclic thioethers, such as ethylene sulfide; irnines,such as ethyleneimine; cyclic carbonates, such as ethylene carbonate;cyclic thiocarbonates, such as ethylene thiocarbonate; cyclicdithiocarbonates, such as ethylene dithiocarbonate; cyclic lactones,such as ε-caprolactone; and cyclic lactams, such as ε-caprolactam.

The molar value of the heterocyclic compound (d), which is to besubjected to addition reaction to the active hydrogen-containingcompound (b) in the presence of the catalyst (c) to give a ring-openingpolymerization product, is generally 1 to 200 moles, preferably 1 to 100moles, per active hydrogen in the active hydrogen-containing compound(b). It is to be adequately selected according to the molecular weightof the ring-opening polymerization product to be prepared and to theintended use thereof.

The level of the catalyst (c) added is not critical but generally is0.0001 to 10% by weight, preferably 0.001 to 1% by weight, relative tothe ring-opening polymerization product to be produced.

It is advantageous to employ the catalyst (c) having a specific chemicalstructure with high steric hindrance as specified by the presentinvention, because this enables to reduce the quantity of catalyst verydrastically as compared with the conventional alkali metal hydroxide andother alkali catalysts (generally used in an amount of 0.1 to 10% byweight).

In subjecting the heterocyclic compound (d) to addition reaction, allthe three, namely the active hydrogen-containing compound (b),heterocyclic compound (d) and catalyst (c), may be charged at once, orthe heterocyclic compound (d) may be added dropwise to a mixture of theactive hydrogen-containing compound (b) and catalyst (c) to therebyeffect the reaction, or the heterocyclic compound (d) and catalyst (c)may be added dropwise to the active hydrogen-containing compound (b) tothereby effect the reaction.

From the viewpoint of reaction temperature control, preferred is themethod comprising adding the heterocyclic compound (d) dropwise to amixture of the active hydrogen-containing compound (b) and catalyst (c),or adding the heterocyclic compound (d) and catalyst (c) dropwise to theactive hydrogen-containing compound (b).

The reaction temperature at which the heterocyclic compound (d) issubjected to addition reaction to the active hydrogen-containingcompound (b) is generally 0° C. to 250° C., preferably 20° C. to 180° C.

The ring-opening polymerization products prepared by the productionmethod of the present invention generally have a number averagemolecular weight of 75 to 100,000, preferably 900 to 20,000. Saidmolecular weight is selected so that it may be suited for the intendeduse:. For instance, when thermosetting resins, for example polyurethaneresins, is to be produced using polyol compositions comprising thepolyoxyalkylene polyols as said ring-opening polymerization product, itis judiciously selected according to the physical characteristicsrequired of the polyurethane resins.

The thus produced ring-opening polymerization product contains thecatalyst (c). According to the use thereof, it may be treated to removethe catalyst (c).

The method of its removal treatment comprises adsorption treatment usingan adsorbent such as a synthetic silicate (magnesium silicate, aluminumsilicate or the like) or activated clay, or neutralization with a basiccompound, for instance.

Even if remaining in the ring-opening polymerization product, thecatalyst (c) of the present invention does not have any significantadverse effect on the reactivity of the polyol and isocyanate in thesubsequent urethane formation reaction, for instance, as compared withthe alkali catalysts in conventional use. From the viewpoint ofcoloration prevention, however, it is preferred that the residualcatalyst be removed.

In particular when ring-opening polymerization products are prepared bysubjecting heterocyclic compounds of the above general formula (5) inwhich Q is —O—and R is a divalent hydrocarbon group of the generalformula (8) below, namely epoxy-containing compounds, to additionreaction to the active hydrogen-containing compound (b) in the presenceof the catalyst (c) according to the present invention, the resultingpolymers have a further marked structural characteristic, namely aproportion of terminal primary hydroxyl groups of not less than 40% andadvantageously not less than 60%.

In the above formula, R² represents a monovalent hydrocarbon groupcontaining 1 to 10 carbon atoms, which may be substituted by a halogenatom or atoms.

As specific examples of the above-mentioned epoxy-containing compounds,there may be mentioned propylene oxide, butylene oxide, laurylene oxide,epichlorohydrin, styrene oxide and the like. Two or more of these may beused in combination. Preferred among these are propylene oxide, butyleneoxide, epichlorohydrin and styrene oxide.

According to its third aspect, the present invention consists in:

a polyol composition (III) for producing thermosetting resins,characterized by comprising the polyoxyalkylene polyol or monool (I)according to the first aspect of the present invention, or;

a polyol composition (II) for producing thermosetting resins, comprisingthe ring-opening polymerization product obtained according to the secondaspect of the present invention. According to its fourth aspect, thepresent invention consists in a thermosetting resin characterized inthat it is derived from said polyol composition (III) and/or said polyolcomposition (II). As said thermosetting resin, there may be mentionedpolyurethane resins and epoxy resins, among others.

The polyurethane resin of the present invention is obtained by reactingthe polyol composition (III) and/or polyol composition (II) with anaromatic isocyanate and/or aliphatic isocyanate (e), if necessary incombination with another polyol component, namely a low-molecular activehydrogen-containing compound (e.g. any of those mentioned as examples ofthe active hydrogen-containing compound in relation to the first aspectof the present invention).

By using, as the polyol components of polyurethane resins, the polyolcomposition (III) and/or polyol composition (II), which contains thepolyoxyalkylene polyol (I) of the present invention as essentialcomponent, characteristic features are introduced that said polyolcomponent is hydrophobic and highly reactive with isocyanate compounds.

Thus, urethane resins derived from the polyol composition (III) and/orpolyol composition (II) of the present invention are characterized inthat the reactivity with isocyanates is high in the step of productionthereof, and that the humidity dependency of resin characteristics(tensile strength, elongation at break, bending strength, etc.) is low.

Furthermore, when such urethane resins are used as coating compositions,they have characteristic features that they are excellent in adhesion topolyolefin rubbers and polyolefin resins, for instance.

Said urethane resins can be used in various forms, such as urethanefoams, urethane elastomers, urethane coating compositions and so on. Asapplications of urethane foams, there may be mentioned cushion materialsfor automobiles, backing materials for automobiles, and the like, and,as applications of the urethane elastomers, there may be mentionedcasting potting materials and the like. As applications of the coatingcompositions, there may be mentioned adhesive or coating compositions orthe like.

BEST MODES FOR CARRYING OUT THE INVENTION

The following examples further illustrate the present invention. Theyare, however, by no means limitative of the scope of the presentinvention.

EXAMPLE 1

A 200-ml SUS autoclave equipped with a stirrer and temperature controldevice was charged with 58.1 g of glycerol-propylene oxide adduct with amolecular weight of 1,000 (Sannix GP-1000, product of Sanyo ChemicalIndustries) and 0.97 g of tris(pentafluorophenyl)borane. Then, 110.1 gof propylene oxide was added dropwise over 12 hours at a reactiontemperature of 70-80° C. Thereafter, the mixture was matured at 75° C.for 6 hours and then neutralized with an aqueous solution of sodiumhydroxide. Then, 3.0 g of synthetic silicate salt (Kyowaad 600, productof Kyowa Chemical) and water were added, and the mixture was treated at60° C. for 3 hours. The mixture was taken out of the autoclave, filteredthrough a 1-micron filter and then dehydrated, to give 161.3 g ofliquid-form polyoxypropylenetriol (molecular weight: 3,000). The yieldwas 97% as calculated based on the weight of glycerol-propylene oxideadduct plus propylene oxide charged. The polyoxypropylenetriol obtainedhad a hydroxyl value of 56.1.

The results of ¹H-NMR chemical shift measurement in terms of δ values ofthe polyoxypropylenetriol obtained (solvent: CDCl₃) are shown below.¹H-NMR, δ values: 1.11 (s, 150.4H), 2.5 (s, 3H), 3.20-3.79 (m, 155.4H)

The proportion of terminal primary hydroxyl groups was determined by the¹H-NMR method described hereinabove and found to be 74%.

The measurement results for ¹H-NMR chemical shift δ values (solvent:CDCl₃) as obtained on that occasion are shown below.

¹H-NMR δ values: 1.13 (s, 150.4H), 3.38-3.83 (m, 153.1H), 9.20-4.39 (m,4.5H), 5.16-5.30 (m, 0.8H)

EXAMPLE 2

A 200-ml SUS autoclave equipped with a stirrer and temperature controldevice was charged with 58.1 g of glycerol-propylene oxide adduct with amolecular weight of 1,000 (Sannix GP-1000, product of Sanyo ChemicalIndustries). Thereto was added dropwise 110.13 g of propylene oxide and0.0008 g of tris(pentafluorophenyl)borane over 12 hours at a reactiontemperature of 714 80° C., and the resulting mixture was matured at 75°C. for 6 hours. Then, 3.0 g of synthetic silicate salt (Kyowaad 1000,product of Kyowa Chemical) and water were added, and the mixture wastreated at 60° C. for 3 hours. The mixture was taken out of theautoclave, filtered through a 1-micron filter and then dehydrated, togive 161.3 g of liquid-form polyoxypropylenetriol (molecular weight:3,000). The yield was 97%. The polyoxypropylenetriol obtained had ahydroxyl value of 56.1.

The results of ¹H-NMR chemical shift measurement in terms of δ values ofthe polyoxypropylenetriol obtained (solvent: CDCl₃) are shown below.

¹H-NMR δ values: 1.11 (s, 150.9H), 2.5 (s, 3H), 3.20-3.79 (m, 155.4H)

The proportion of terminal primary hydroxyl groups was determined by the¹H-NMR method described hereinabove and found to be 75%.

The measurement results for ¹H-NMR chemical shift δ values (solvent:CDCl₃) as obtained on that occasion are shown below.

¹H-NMR, δ values: 1.13 (s, 150.4H), 3.38-3.83 (m, 153.1H), 4.20-4.39 (m,4.5H), 5.1-5.30 (m, 0.8H)

EXAMPLE 3

The procedure of Example 1 was followed in the same manner except that87,1 g of glycerol-propylene oxide adduct with a molecular weight of3,000 (Sannix GP-3000, product of Sanyo Chemical Industries) was used inlieu of the glycerol-propylene oxide adduct with a molecular weight of1,000, and that tris(pentafluorophenyl)borane and propylene oxide wereused in an amount of 0.97 g and 87.1 g, to give 169.0 g of liquid-formpolyoxypropylenetriol (molecular weight: 6,000). The yield was 97%. Thepolyoxypropylenetriol obtained had a hydroxyl value of 28.1.

The results of ¹H-NMR chemical shift measurement in terms of δ values ofthe polyoxypropylenetriol obtained (solvent: CDCl₃) are shown below.

¹H-NMR, δ values: 1.11 (s, 305.6H), 2.5 (s, 3H), 3.20-3.79 (m, 310.6H)

The proportion of terminal primary hydroxyl groups was determined by the¹H-NMR method described hereinabove and found to be 74%.

The measurement results for ¹H-NMR chemical shift δ values (solvent:CDCl₃) as obtained on that occasion are shown below.

¹H-NMR δ values: 1.13 (s, 305.6H), 3.38-3.83 (m, 308.3H), 4.20-9.34 (m,4.5H), 5.16-5.30 (m, 0.8H)

EXAMPLE 4

The procedure of Example 2 was followed in the same manner except that87.1 g of glycerol-propylene oxide adduct with a molecular weight of3,000 (Sannix GP-3000, product of Sanyo Chemical Industries) was used inlieu of the glycerol-propylene oxide adduct with a molecular weight of1,000, and that propylene oxide and tris(pentafluorophenyl)borane wereused in an amount of 87.1 g and 0.0009 g, to give 169.0 g of liquid-formpolyoxypropylenetriol (molecular weight: 6,000). The yield was 97%. Thepolyoxypropylenetriol obtained had a hydroxyl value of 28.1.

The results of ¹H-NMR chemical shift measurement in terms of δ values ofthe polyoxypropylenetriol obtained (solvent: CDCl₃) are shown below.

¹H-NMR, δ values: 1.11 (s, 305.6H), 2.5 (s, 3H), 3.20-3.79 (m, 310.6H)

The proportion of terminal primary hydroxyl groups was determined by the¹H-NMR method described hereinabove and found to be 74%.

The measurement results for ¹H-NMR chemical shift δ values (solvent:CDCl₃) as obtained on that occasion are shown below.

¹H-NMR, δ values: 1.13 (s, 305.6H), 3.38-3.83 (m, 308.3H), 4.20-4.39 (m,4.5H), 5.16-5.30 (m, 0.8H)

EXAMPLE 5

The procedure of Example 2 was followed in the same manner except that87.1 g of polypropylene glycol with a molecular weight of 1,000 (SannixPP-1000, product of Sanyo Chemical Industries) was used in lieu of theglycerol-propylene oxide adduct with a molecular weight of 1,000, andthat propylene oxide and tris(pentafluorophenyl)borane were used in anamount of 87.1 g and 0.0009 g, to give 169.0 g of liquid-formpolyoxypropylene glycol (molecular weight: 2,000). The yield was 97%.The polyoxypropylenetriol obtained had a hydroxyl value of 55.9.

The proportion of terminal primary hydroxyl groups was determined by the¹H-NMR method described hereinabove and found to be 72%.

EXAMPLE 6

A 200-ml SUS autoclave equipped with a stirrer and temperature controldevice was charged with 139 g of propylene dithiocarbonate and 8.79 g oftris(pentafluorophenyl)borane, and the reaction was carried out at areaction temperature of 120° C. for 12 hours. The mixture was thenmatured at 120° C. for 6 hours. The reaction mixture was poured into 500g of n-hexane, whereupon poly propylene dithiocarbonate) precipitated.This precipitate was filtered off, whereby 109 g of poly propylenedithiocarbonate) was obtained. The yield was 81% as calculated based onthe weight of propylene dithiocarbonate charged. The thus-obtained polypropylene dithiocarbonate) had a molecular weight of 18,500.

Comparative Example 1

Using 0.63 g of potassium hydroxide in lieu oftris(pentafluorophenyl)borane, to the same reaction apparatus as used inExample 1 was added dropwise 110.1 g of propylene oxide over 12 hours ata reaction temperature of 120-130° C. The mixture was then matured at120° C. for 6 hours. Then, 3.0 g of synthetic silicate salt (Kyowaad600, product of Kyowa Chemical) and 2 g of water were added and themixture was treated at 60° C. for 3 hours. The mixture was taken out ofthe autoclave, filtered through a 1-micron filter and then dehydrated togive 161.3 g of liquid-form polyoxypropylenetriol (molecular weight:3000). The yield was 97%. The thus-obtained polyoxypropylenetriol had ahydroxyl value of 56.1.

The results of ¹H-NMR chemical shift measurement in terms of δ values ofthe polyoxypropylenetriol obtained (solvent: CDCl₃) are shown below.

¹H-NMR, δ values: 1.11 (s, 150.4H), 2.5 (s, 3H), 3.20-3.79 (m, 155.9H)

The proportion of terminal primary hydroxyl groups was determined by the¹H-NMR method described hereinabove and found to be 2%.

The measurement results for ¹H-NMR chemical shift δ values (solvent;CDCl₃) as obtained on that occasion are shown below.

¹H-NMR, δ values: 1.13 (s, 150.4H), 3.38-3.83 (m, 155.4H), 4.20-4.34 (m,0.1H), 5.16-5.30 (m, 2.9H)

Comparative Example 2

The procedure of Example 6 was followed in the same manner except that2.4 g of BF₃ etherate was used in lieu of tris(pentafluorophenyl)borane,to give 54 g of poly propylene dithiocarbonate). The yield was 59% ascalculated based on the weight of propylene dithiocarbonate charged. Thethus-obtained poly (propylene dithiocarbonate) had a molecular weight of16,700.

Production Example 1

A mixture was prepared by uniformly mixing 439.9 g of thepolyoxypropylenetriol (molecular weight: 3,000) obtained in Example 1,219.2 g of tolylene diisocyanate, 18.7 g of water, 0.57 g of stannousoctoate, 5.26 g of dioctyl phthalate, 5.3 g of polyoxypropylene glycol(molecular weight: 2,000), 0.33 g of triethylenediamine, 2.2 g ofN-methylmorpholine and 6.6 g of foam modifier (L-520, product of NipponUnicar). This mixture was poured uniformly into a vessel (30 cm×30 cm)and allowed to expand to give a urethane foam.

As for the foaming behavior on that occasion, the 100% rise time was 1minute. The viscosity at the time of foaming was checked by means of avibration viscometer. It was found that the viscosity of the foamingresin arrived at 100,000 cps in 40 seconds after mixing.

Comparative Production Example 1

A urethane foam was produced in the same manner as in Production Example1 except that 934.9 g of the polyoxypropylenetriol (molecular weight:3,000) produced in Comparative Example 1 was used in lieu of thepolyoxypropylenetriol (molecular weight: 3,000) produced in Example 1.

As for the foaming behavior on that occasion, the 100% rise time was 3minutes. The viscosity at the time of foaming was checked by means of avibration viscometer. It was found that the viscosity of the foamingresin arrived at 100,000 cps in 60 seconds after mixing.

Production Example 2

A 500-ml four-necked flask equipped with a stirrer and a temperaturecontrol device was charged with 115.2 g of4,4′-diphenylmethanediisocyanate, 264.9 g of the polypropylene glycol(molecular weight: 2,000) obtained in Example 5 and 20.9 g of ethyleneglycol, and the reaction was carried out at 68° C. for 5 hours to give apolyurethane elastomer. During the reaction, the percent reaction(percent consumption) of the isocyanato groups was 72% after 1 hour, 93%after 2 hours and 100 after 2.5 hours.

The weight average molecular weight, number average molecular weight (asdetermined by gel permeation chromatography), tensile strength at breakand elongation at break of the polyurethane elastomer obtained are shownin Table 1.

Comparative Production Example 2

A polyurethane elastomer was produced in the same manner as inProduction Example 2 except that polypropylene glycol with a molecularweight of 2,000 (Sannix PP-2000, product of Sanyo Chemical Industries;hydroxyl value: 55.9; proportion of terminal primary hydroxyl groups: 2%was used in lieu of 269.9 g of the polypropylene glycol (molecularweight: 2,000) obtained in Example 5.

During the reaction, the percent reaction (percent consumption) of theisocyanato groups was 49% after 1 hour, 79% after 2 hours, 93% after 3hours, 98% after 4 hours and 100% after 5 hours.

The molecular weights, tensile strength at break and elongation at breakof the polyurethane elastomer obtained are shown in Table 1.

TABLE 1 Compar. Ex. 2 Ex. 2 Weight average molecular weight 210,000170,000 Number average molecular weight 91,000 74,000 Tensile strengthat break (kg/cm²) 437 286 Elongation at break (%) 760 750

As is evident from comparison between Examples 1 and 2 and ComparativeExamples 1 and 2, the polyoxyalkylene polyols (I) of the presentinvention have higher reactivity with isocyanato groups, as comparedwith the conventional polyoxyalkylene polyols.

Further, as shown in Table 1, the polyurethane elastomers derived fromthe polyoxyalkylene polyols (I) of the present invention have excellentphysical resin characteristics, namely they have higher molecularweight, and higher tensile strength at break, though equivalent inelongation at break, as compared with the comparative examples.

INDUSTRIAL APPLICABILITY

According to the present invention, ring-opening polymerization productscan be produced from heterocyclic compounds in good yields. Inparticular when alkylene oxides are subjected to ring-openingpolymerization, polyoxyalkylene polyols excellent in reactivity areobtained without impairing their hydrophobicity. By using thesepolyoxyalkylene polyols as polyol components, it is possible to obtainthermosetting resins having high rates of reaction and excellent inphysical resin characteristics (tensile strength, bending strength) andwhose physical properties are not deteriorated by moisture.

The polyoxyalkylene polyols and monools of the present invention areuseful also as raw materials for the production of textile treatmentoils, detergents, antifoaming agents and other surfactant compositions.

What is claimed is:
 1. A polyoxyalkylene polyol or monool (I) of thegeneral formula (1) below, wherein greater than 60% of the terminallylocated hydroxyl-containing groups, namely —AO—H groups, are primaryhydroxyl-containing groups of the general formula (2) below asdetermined by ¹H-NMR measurement; R¹—[—(ZO)_(p)—(AO)_(q)—H]_(m)(1)

wherein: in the formula (1), R¹ is a group having a valence of m asderived from a compound selected from the group consisting of water, analcohol compound, a phenol compound, an amino-containing compound, acarboxyl-containing compound, a thiol-containing compound and aphosphoric acid compound by removal of its active hydrogen atom oratoms; Z is an alkylene group containing 2 to 12 carbon atoms or acycloalkylene group containing 6 to 12 carbon atoms, each of which maycontain at least one halogen atom or aryl group or both as substituents;A is an alkylene group containing 3 to 12 carbon atoms or acycloalkylene group containing 6 to 12 carbon atoms, each of which maycontain at least one halogen atom or aryl group or both as substituents;m is an integer of 1 or 2 to 100; p is an integer of 1 or more when m isan integer of 1, or an integer of 0 or 1 or more when m is an integer of2 to 100 and q is an integer of 1 or more, p+q being equal to 1 to 200;and in the formula (2), R² is an alkyl group containing 1 to 10 carbonatoms or an aryl group containing 6 or 10 carbon atoms, each of whichmay be substituted by a halogen atom or atoms.
 2. The polyoxyalkylenepolyol or monool (I) according to claim 1, wherein R¹ is a group derivedfrom water, an alcohol compound or an amino-containing compound byremoval of its active hydrogen atom or atoms.
 3. The polyoxyalkylenepolyol or monool (I) according to claim 1 wherein not less than 72% ofthe terminally located hydroxyl-containing groups, namely —AO—H groups,are primary hydroxyl-containing groups of the general formula (2), asdetermined by ¹H-NMR measurement.
 4. A polyol composition (III) whichcomprises a polyoxyalkylene polyol or monool (I) according to claim 1.5. The polyol composition (III) according to claim 4, which is intendedfor use as a polyol composition for producing thermosetting resins. 6.The polyol composition (III) according to claim 5, wherein saidthermosetting resins are polyurethane resins.
 7. The polyol composition(III) according to claim 4, which is intended for use as a polyolcomposition for producing surfactants.
 8. A method of producingring-opening polymerization products, which comprises subjecting aheterocyclic compound (d) of the general formula (5) below toring-opening addition polymerization with an active hydrogen-containingcompound (b) of the general formula (3) below in the presence of atleast one catalyst (c) selected from the group consisting of compoundshaving the general formula (4-1) below, compounds of the general formula(4-2) below and compounds of the general formula (4-3) below:R¹—[—(ZO)_(p)—H]_(m)  (3) X—(—R³)₂  (4-1)

wherein in the formula (3), R¹ is a group having a valence of m asderived from a compound selected from the group consisting of water,alcohol compound, a phenol compound, an amino-containing compound, acarboxyl-containing compound, a thiol-containing compound and aphosphoric acid compound by removal of its active hydrogen atom oratoms; Z is an alkylene group containing 2 to 12 carbon atoms or acycloalkylene group containing 6 to 12 carbon atoms, each of which maycontain at least one halogen atom or aryl group or both as substituents;m is an integer of 1 or 2 to 100; and p is an integer of 0 or 1 to 199;in each of formulae (4-1), (4-2) and (4-3), X represents a boron atom oraluminum atom; F represents a fluorine atom; and R³ represents asubstituted or unsubstituted phenyl group of the general formula (6)below and/or a tertiary alkyl group of the general formula (7) below:

wherein Y represents a hydrogen atom, an alkyl group containing 1 to 4carbon atoms, a halogen atom, a vitro group or a cyano group; and krepresents an integer of 0 to 5, provided that when k is 2 or more, aplurality of Y groups may be the same or different;

wherein R⁴, R⁵ and R⁶ each independently represents an alkyl groupcontaining 1 to 4 carbon atoms and when there are a plurality of R³groups, they may be the same or different; and in the formula (5), R isan alkylene group containing 3 to 12 carbon atoms, which may contain atleast one halogen atom or aryl group or both as substituents; Q is adivalent organic group selected from the group consisting of —O—, —S—,—NH—, —O(CO)O—, S(CO)O—, —O(CS)O—, —O(CO)S—, —O(CS)S—, —S(CS)O—,—S(CO)S—, —S(CS)S—, —COO—, —CSO—, —COS—, —CSS—, —CONH—and —N═C(—R⁷)—O—in which R⁷ represents an alkyl group containing 1 to 12 carbon atoms, acycloaclyl group containing 3 to 12 carbon atoms, which may besubstituated by an alkyl group, or an aryl group containing 6 to 12carbon atoms, which may be substituated by a halogen atom or atoms. 9.The production method according to claim 8, wherein, in the formula (5)representing a heterocyclic compound (d), Q is —O—and R is a divalenthydrocarbon group of the formula (8) below:

wherein R² represents a monovalent hydrocarbon group containing 1 to 10carbon atoms, which may be substituted by a halogen atom or atoms. 10.The production method according to claim 9, for producing thering-opening polymerization product in which not less than 40% of theterminal hydroxyl groups are primary hydroxyl groups.
 11. The productionmethod according to claim 9, for producing the ring-openingpolymerization product in which not less than 60% of the terminalhydroxyl groups are primary hydroxyl groups.
 12. A ring-openingpolymerization product obtained by the production method according toclaim 8, wherein not less than 60% of the terminally locatedhydroxyl-containing groups are primary hydroxyl-containing groups of thegeneral formula (2) as determined by ¹H-NMR measurement;—CH(—R²)—CH₂OH  (2) in the formula, R² is an alkyl group containing 1 to10 carbon atoms or an aryl group containing 6 to 10 carbon atoms, eachof which is optionally substituted by a halogen atom or atoms.
 13. Apolyol composition (II) for producing thermosetting resins, whichcomprises a ring-opening polymerization product prepared by theproduction method according to claim
 9. 14. The polyol composition (II)according to claim 13, intended for use in polyurethane resinproduction.
 15. A method of producing polyurethane resins by reacting apolyol component and a polyisocyanate (e), wherein said polyol componentis the polyol composition (II) according to claim
 14. 16. A polyurethaneresin obtained by reacting a polyol component and a polyisocyanate (e),wherein said polyol component is the polyol composition (III) accordingto claim
 6. 17. A polyol composition (III) which comprises apolyoxyalkylene polyol or monool (I) according to claim
 2. 18. A polyolcomposition (III) which comprises a polyoxyalkylene polyol or monool (I)according to claim
 3. 19. A polyol composition (II) for producingthermosetting resins, which comprises a ring-opening polymerizationproduct prepared by the production method according to claim 10.